CA2241800A1 - Process for producing cellulose derivatives - Google Patents

Abstract

Disclosed is a method for producing cellulose derivatives wherein cellulose is impregnated with an alkali solution, the impregnated cellulose is selectably pressed out, and the cellulose undergoes a substitution or addition reaction, whereby the cellulose derivative is obtained with a degree of substitution DS.
The applied cellulose is an ammonia activated cellulose. The molar ratio of the alkali to the AHG (anhydro glucose unit) in the cellulose at the beginning of the substitution or addition reaction does not exceed twice the valve of the desired DS. For the swelling of cellulose, no excess of alkali is required, which does not react to produce alkali cellulose but only adheres to the cellulose as a loose association product. Reagent consumption in the substitution or addition reaction is lower. Fewer secondary products are formed.

Description

~ CA 02241800 1998-07-03 ,~ ~

,, Process for producin~ cellulose derivatives The invention relates to a process for producing cellulose derivatives, with which the cellulose is impregnated with an aLIcali solution, the impregnated cellulose is optionally pressed and the cellulose is subjected to a substitution or addition reaction, wherein a cellulose derivative witll a substitution degree DS is obtained.

Most substitution reactions of cellulose take place via alkali cellulose as intermediate stage. Here a distinction is made bet~,veen reactions with alkali consumption, e.g. the production of methyl or ethyl cellulose by reaction with the corresponding aL~;yl halogenides, the production of carboxy-methyl cellulose by reaction with chloracetic acid or its sodium salt, or the production of cell~llose xanthogenate by reaction with carbon disulphide, and reactions without alkali consumptiQn, e g= the produç~ion of hydrsxy-ethyl ~nd hydroxy-prQpyl cellulose by reaction of the alkali cellulose with ethylene o~ide or propylene oxide, or the production of cyano-ethyl cellulose by reaction with acrylonitrile.

Cleaned cellulose is converted to alkali cellulose by treating it ~ith alkali, in the industry practically e~clusively soda lye (alkalisation). It is assumed that in the aLkali cellulose part of the cellulose is present in the form of a hydrated alcoholate Cell-O~a+ ... H~ O~. The soda lye furtherrnore serves to s~,vell the cellulose and make it accessible to the reaction partners of the subsequent derivation reactions.
In the amorphous part of the cellulose the cellulose alcoholate is formed relatively easily. So that this will also occur for the crystalline part of the cellulose, certain conditions must be maintained with regard to the temperature and concentration of the soda lye. Only when the concentration of soda lye is sufficiently high, will the lattice of soda cellulose I be forrned, which durin~ the washing (regeneratin~) changes over to the lattice of cellulose II (regenerated cellulose). During the conversion of cellulose I to soda cellulose I, the distances of the 101-lattice planes of about 7 are widened to appro~imately 12 A. This change can also be noted by looking at the apparent density. Cellulose material with a high crystallinity has a k~6 SWORN TRANSLAT~,~
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~ CA 02241800 1998-07-03 high resistance to ~lk~ tion. In practice only a narrow NaOH-concentration range produces alkali celluloses suitable for industrial use. With the known industrial processes the pre-comminuted cellulose is immersed in 18-20% aqueous soda Iye (Iye ratio at least 10:1). A large part of tl~e soda Iye is subsequently removed again by pressing. However, when doing so normally a composition of approximately 34% by mass cellulose and 66% by mass aqueous NaOH (steeping and pressing) is obtained or of only 25% by mass cellulose and 75% by mass NaOH (slurry and roller press).

A large part of the soda lye rem~ining behind in this cellulose is, however, notused for the subsequent derivation reactions, but adheres as loose associate to the cellulose and is not removed during the pressing. A w:~hin~ out with water is not possible, as this dilutes the soda lye and the initial modification would again occur.

The amount of soda lye which is excess for the production of the cellulose derivatives causes during the derivation reactions a high reagent consumption, which generally is associated with a salt formation and the formation of by-products. During the xanthogenation the excess soda lye reacts with carbon disulphide to, for example, the undesirable trithio-carbonate. The salts as well as the by-products must be separated, to some extent at high expense and must be disposed of or processed. For the cellulose ethers, the costs for this already amo~mt to 70% of the production costs. For the production of viscose via cellulose xanthogenate, because of the strict of~cial environmental protection requirements, considerable costs are also required for cleaning the waste water.
Notwithstanding the high excess of soda lye used with the known process, it is found that in the derivatives produced via alkali cellulose as intermediate stage, inhomogeneous substituent distributions are present. In cellulose ethers these can be noted, for example, by a too low solubility, a to<) great turbidity and a too low flocculation temperature.

I E
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~ER .F R~ . SPA . OU~, ~ CA 02241800 1998-07-03 It has already been reported that with activated cellulose compared to untreatedcellulose, the lattice conversion from cellulose I to soda cellulose I takes place already at a considerably lower NaOH concentration. In this connection ~ve referto Schleicher, Daniels and Philipp, in "Faserforschung ~md Textiltechnik" 24 (1973) p. 371 to 376 and WO 96/30411. However, these publications do not suggest that with a view to the subsequent derivation reactions the absolute quan-tity of alkali, i.e. the molar NaO~/AHG ratio (AHG = anhydroglucose unit), couldplay a role.

It was, therefore, the object of the invention to make available a process mentioned at the outset, which does not have the indicated disadvantages of the state of the art. It ~as a particular object of the invention to make available a process of the type mentioned at the outset, with ~,vhich at the beginning of the derivation reaction only a small e~cess or a stoichiometric or even a sub-stoichiometric quantity of alkali is present.

According to the invention this object is achieved by a process for producing cellulose derivatives with which a) cellulose is impregnated with an alkali solution, b) the impregnated cellulose is optionally pressed and c) the cellulose is subjected to a substitution or addition reaction, ~ herein a cellulose derivati~e ~ith a substitution degree DS is obtained, which is characterised in that the cellulose used is an ammonia-activated cellulose and the molar ratio of aLkali to AHG in the cellulose at the beginning of step c) does not e~ceed ~ times the DS.

To be understood under "alkali solution" are aqueous or alcoholic solutions of aL~cali metal or ~lk~line earth metal hydro~cides, o~ides andlor carbonates.
Preferably, the aLkali solution is aqueous or alcoholic soda lye or potassium lye.
The alcoholic solutions preferably contain methanol, ethanol and/or isopropanol as solvent.

~f S~T I E
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~ CA 02241800 1998-07-03 ., ~

With processes according to the invention, alkali solutions with a low concen-tration are already effective since for the successful further conversion a transformation by alkali to the cellulose II-lattice is not necessary, seeing that as a result of the activation a new cellulose modification ~ith widened lattice has already occurred. Generally, concentrations of approximately 12% by mass or less are suitable. Preferably, the alkali solution has a concentration of less than approximately 10, in particular less than approximately 8% by mass. Concen-trations of approximately 1 to 6% by mass are particularly suitable.

The molar aL~;ali/AHG ratio at the beginning of step c) does not e~ceed 2 times,preferably 1.5 times, in particular 1.1 times the desired substitution degree. In particular, in the case of aL~ali-consuming reactions a stoichiometric aL~ali/AHG
ratio can be used. To be understood under stoichiometric is a molar aL~alilAHG
ratio which lies close to the desired substitution degree of the end product.

With reactions which are only catalysed by alkali, it is even possible to use a sub-stoichiometric ratio with respect to the desired substitution degree.

The substitution or addition reaction can preferably be brought about by reaction with carbon disulphide, acyl-group transferring reagents, such as carbo~ylic acid anhydrides, e.g. acetic anhydride, isopropenyl acetate, dicarboxylic acid anhydrides, e.g. phthalic anhydride, succinic anhydride, glutaric anhydride, maleic anhydride, carboxylic acid chlorides, e.g. propionic chloride, stearylic chloride, carbo~ylic acids, e.g. formic acid; aL~yl-group transferring reagents such as methyl chloride, ethyl chloride, ben~zyl chloride; aL~ene oxides, such as ethylene oxide, propylene o~ide, styrene o~cide; a-halocarboxylic acids, such as chloracetic acid, or their salts, cc"~-unsaturated carbonyl compounds or acrylonitrile. In addition, sometimes a catalyst such as, for example, benzyl trimethyl ammonium chloride, tetrabut l ammonium chloride, -hydroxide, hydrogen sulphate, Ti(OR)~, imidazole, N-methyl imidazole, Li-, Na- and Mg-acetate is advantageous. The }~n E
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~ CA 02241800 1998-07-03 reaction can take place in an aqueous medium or an organic solvent, such as NMP,DMAc, DMSO, DMF, dioxan, THF, iso-propanol, tert-butanol or mi~;tures thereof.

With the process according to the invention ammonia-activated cellulose must be used. "Ammonia activation" means that the cellulose has been treated under high pressure with liquid arnmonia and subsequently the pressure of the system has been released. Native cellulose is a polysaccharide which, because of the formation of intermolecular hydrogen bridge bonds, comprises crystalline parts.
The ammonia molecule, because of its nucleophilic properties, is able to push itself between the cellulosic OH-groups. This ensures a swelling and widening ofthe lattice. D~lring the subsequent pressure release the ammonia evaporates for the greater part. When doing so, the degree of swelling or the widening of the lattice decreases again and assumes a value between the complete swelling and tlle untreated cellulose. The known processes for the ammonia activation of cellulosecan be divided into the simple ammonia e~pansion and the so-called ammonia explosion. With both the cellulose is treated with liquid ammonia in a pressure vessel. With the ammonia expansion technology, by opening a valve with a small bore on the pressure reactor, it is ensured that under a reduction of the pressure part of the liquid ammonia escapes from the pressure vessel in the gaseous form.The cellulose rem~ining behind in the pressure reactor does not release all the liquid ammonia, but approximately 50~iO of the ammonia used remains behind in the cellulose. Such a process is described, for example, in the DE 43 29 937 Cl.With the ammonia explosion technology, the volume available to the system cellulose/liquid ammonia is increased in an e~plosion-like manner whilst reducing the pressure. For the practical implementation thereof, on the pressure reactor a valve with a large bore can be opened, when the cellulose and ammonia are flung in sudden bursts out of the pressure tank into an e~plosion or collecting charnber.
With this the greater part of the ammonia evaporates from the cellulose; only a small residual ammonia content remains behind, the amount of which depends on the process parameters.

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' CA 02241800 1998-07-03 .. . .

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For the purposes of the invention the activated cellulose preferably has a LODP-value ~"Limiting Degree of Polymerisation" or "Levelling-off Degree of Polymer-isation" (LODP-value); see Hans A. Krassig "Polymer Monographs", Vol. 11, Gordon and Breach Science Publishers, in particular p. 191 et seq.) of between approximately 100 and 160 and in particular between approximately 120 and 145.
Preferably, the activated cellulose is in the form of fluff and is characterised by a low density of less tllan approximately 0.2 g/cm3, in particular less than appro-ximately 0.1 g/cm3. Activated cellulose had a widened space-reticular structure as well as a high specific surface with high accessibility.

Preferably, the activated cellulose is obtained by a process with which the cellulose is brought into contact with liquid ammonia at an initial pressure higher than atmospheric pressure and at a temperature of at least approximately 25~C, whereir. the quar~tity of the liquid ammonia suffices at least to wet the sl~..ce of the cellulose and the volume available to the system cellulose/liquid ammonia isincreased in an explosion-like manner ~,vhilst reducing the pressure by at least S
bar.

When the term "explosion-like" is used here, this must be seen in the narrow sense. Preferably, the e~cplosion-like increase in volume takes place within less than one second, in particular less than 0.5 seconds. A continuous process is based on an incremental celluloselliquid ammonia quantity. The cellulose preferably isbrought into contact with the liquid ammonia in a pressure device, and the pressure of the system cellulose/liquid arnmonia is reduced by transferring it into an explosion chamber with a volume that is larger than that of the pressure device.
Preferably, the starting pressure lies between appro~imately S and 46 bar, in par-ticular between appro~imately ~5 and 30 bar. The minimum drop in pressure of S
bar is critical. Below this no adequate activation of the cellulose will be obtained.
E~ceeding the upper limit value of appro~irnately 46 bar will not result in further advantages. The obtaining of such a value requires a relatively great amount of apparatus, so that from a practical point of view a further increase does not make A~ E
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G E R .F RE . SP A . O U T , ~ CA 02241800 1998-07-03 sense. The temperature of approximately 25 to 85~C or 55 to 65~C correlates withthe indicated pressure frame. Preferably, the starting pressure in the system cellulose/liquid ammonia is reduced in an explosion-like manner by at least approximately 10 bar and, in particular, approximately 30 bar. Preferably, the explosion takes place in an explosion chamber which is kept under vacuum. This explosion chamber must be chosen sufficiently large so as to obtain in the largevolume the desired separation into fibres or defibrillation. Preferably, the ammonia is drawn off from the explosion chamber, condensed again and fed back into the process.

A sufficient quantity of ammonia must be pressed into the pressure device, so that under the pressure and temperature conditions required according to the invention liquid arnmonia will be present and at least the surface of the cellulose is wetted.
Preferably per 1 part by mass of cellulose at least approximately 1 part by mass, in particular approximately S to 10 parts by mass of liquid ammonia are used. As a result of the ammonia an at least partial swelling of the cellulose takes place.
The preferred activation process can be carried out discontinuously or continuous-ly. With the discontinuous process the apparatus essentially comprises a pressure tank which can be filled with the material to be treated, and a collecting or e~pan-sion tank connected to same by way of a valve. Here it must be ensured that the valve, when open, has a large opening so that during the explosion the cellulosematerial will not dam up and not only ammonia will escape. The expansion tank has a much larger volume than the pressure tank, e.g. the volume of the pressuretank is 1 1 and the volume of the e~;pansion tank 30 1. The pressure tank is provided with a feed pipe for ammonia, optionally with the interposition of a pressure-increasing device. To ensure a further increase in pressure, in addition a feed pipe for inert gases, e.g. nitrogen, may be provided.

The process can be carried out in a continuous manner, using a tubular or cylinder shaped, pressure-resistant reactor, with which the bringing into contact of the ~~C~ E
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' CA 02241800 1998-07-03 cellulose and liquid ammonia takes place in the cylinder of the reactor and the impregnated material is transported through the reactor with the aid of a conveyor screw in the form of a wad and is discharged intermittently through a valve or asuitable system of pressure locks into a collecting chamber. Suitable components, which the expert can easily adapt for carrying out the process according to the invention, are described inthe EP-A-329 173 andthe US-4 211 163 respectively.

Thç cellulose should have a low moisture content, preferably less than 9% by mass, in particular less than 7% by mass. Preferably it is chemically pure, i.e.~refer~bly it contains less than approximately 12, in particular less than approximately 8% by mass of foreign substances. The contact time between the liquid ammonia and the cellulose is not critical. As an expedient minimum contact time appro~imately 4 minutes can be indicated; as a rule it amounts to approximately 8 minutes.

An activated cellulose produced by ammonia explosion has a special X-ray diffraction spectrum with peaks at the following diffraction angles 2 ~ and withthe relative intensities:
Peak 1 1,25 + 1 of the relative intensity of appro~imately 15 to 25, Peak 17 + 1 of the relative intensity of appro~imately 25 to 40 and Peak 20,5 + 1 of the relative intensity 100 (reference value).

This cellulose modification is also called cellulose III~. It was found that during the treatment of this cellulose modification with 4 to 12% by mass soda lye, a mixture of cellulose II and amorphous cellulose is obtained, wherein the portion of the amorphous cellulose increases with the concentration of the used soda lye.
During the conventional mercerisation, i.e. the treatment of native cellulose with 18 to 20% by mass soda lye, from the cellulose I first alkali cellulose and fromthis cellulose II, but never amorphous cellulose, is obtained. During the treatrnent SWORN TRANSLAT~R
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' CA 02241800 1998-07-03 of cellulose III* with soda lye of a concentration of less than 4% by mass, in particular less than 2% by mass, probably an addition compound of cellulose III*and NaOH is formed.

The following explanations are given with special reference to the ammonia explosion and aqueous soda Iye, but apply correspondingly to other activation processes, alkalis and solvents.

For the treatment witll aqueous soda Iye, the residual ammonia content of the cellulose after the NH3-explosion is not critical. After the NH,-explosion the ammonia-activated cellulose is brought into contact with diluted soda lye in a suitable manner. To this end, the cellulose can be fed into a solution of the lye in ~vater or can be sprayed with the solution, or the solution can be passed through the cellulose in counter-current. All technological embodiments of the bringing into contact of a solid substance with a liquid component, which lead to a thorough mixing or penetration, are conceivable and possible here.

The high accessibility of the NH3-exploded cellulose as well as its high specific surface (low density) perrnit the quick diffusion of the NaOH-solution into the inside of the cellulose, resulting in a homogeneous distribution of the NaOH
through the entire cellulose. The NH3-exploded cellulose is included by the diluted NaOH-solution.

In doing so the NaOH-molecules displace the NH3-molecules that are still present, forming the known polar structure with the celiulosic OH-groups, since due to the higher basicity of the NaOH the ammonia is expelled from the cellulose.

Accordingly there exists the following "task distribution": the arnmonia explosion produces a high accessibility of the cellulose, and the NaOH forms dipoles with the cellulosic OH-groups.

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-The advantages of the splitting up of the activation or the increase in t~e accessibility on the one side and of the formation of aL~ali cellulose on the other side, are obvious. The activation, preferably by ammonia explosion, constitutes an essential prerequisite for the production of stoichiometric alkali cellulose. The advantages of the formation of stoichiometric aL~cali cellulose and of the cellulose derivatives produced from same can be sl-mm~rised as follows:

In contrast to the conventional mercerisation or ~lk~ tion, less or no a&ering, i.e. e~cess Iye occurs. Aceordingly, the process step of pressing out the Iye can optionally be dispensed with. The consumption of NaOH can, therefore, be drastically reduced (up to 75%). Closely associated therewith are a lower con-sumption of reagents, an increased yield and a lower salt and by-product formation.

The reactions, although still carried out hetero~eneously, approach a homogeneous pattern. As a result, also a higher product quality and performance is obtained for the end products, which can be attributed to a more homogeneous substituent distribution. This in turn is the result of a homogeneous distribution of the cellulose-o~onium-NaOH-complexes .

In the following the advantages will be e~plained with reference to the production of viscose:

For the ammonia explosion the cellulose need only be pre-comminuted relatively coarsely ~torn up). As a result of the NH3-e~plosion the cellulose is then to a far reaching e~tent separated into ~lbres, so that a filrther mechanical comminuting(shredding) can be dispensed with, which means a considerable saving of energy.
When using cellulose with a polymerisation degree close to that which is to be obtained for the end product, also the so-called ripeness is not required. With regard to the production of viscose this is a relati~ ely tricky process step, since A~D)~ E
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' CA 02241800 1998-07-03 during same the risk of a drying out of the cellulose crurnbs e~ists, which inevitably results in inhomogeneous reactivities.
During the production of xanthogenate by the process according to the invention,the for example ammonia-exploded cellulose is fed into 5-6% NaOH, the lye ratio being chosen in such a way that after the complete dissolving an 8-9% viscose isobtained. This corresponds to the cellulose xanthogenate concentration customaryduring spinning. The formation of the xanthogenate takes plays whilst stirring or shearing and slowly adding CS2, when during the course of the reaction in-creasingly larger portions of cellulose are dissolved. The monitoring of the dissolving process by suitable technical means (optical sensors, viscosity, torque etc) permits the use of only as much carbon disulphide as is required. The reaction takes place more quickly than with the conventional process. As a result, with existing plants an up to 30% higher production capacity can be obtained.

Alternatively, the for example ammonia-e~ploded cellulose can be brought into contact with only 1-2% NaOH, after which carbon disulphide is added and parallelto the adding of the carbon disulphide or after completing the adding of the carbon disulphide, the spinning concentration of the viscose can be adjusted with concen-trated ~aOH.

In the following e~amples all percentage data are % by mass, unless otherwise indicated.

E~ample 1: Production of ammonia-e~ploded cellulose 200 g commercial cellulose (Cuo~am - DP 480) with an a-cellulose content of appro~imately 96%, in sheet form (water eontent appro~imately 8%) was cut Up into approximately 1.3 x 1.3 cm pieces and p~lt into an autoclave of 1 1 with a double wall for steam heating. Subsequently 400 g liquid ammonia were pressed into the autoclave throu~h a valve. The mass ratio ammonia/cellulose was 2:1. Bythe stearn heating of the autocla~,e the temperature was increased to 60~C. Thisresulted in a pressure inside the autoclave of appro~cimately 20 bar. The reaction AC~)~R~ E
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'~ RRF.SPA.~UT, ~ CA 02241800 1998-07-03 -mixture was kept under these conditions for 60 s. Subsequently, by opening the valve (inside diameter 4 cm), the mixture was suddenly and completely released into an explosion tank with a volume of 30 1. An optimum defibrillation took place. The ~tr,monia corter.t of the product occ~rn:ng jn the explosion chamber amounted to approximately 1% by mass, related to the de~lbrillated cellulose.

Example 2: Production of benzvl cellulose This NH3-activated cellulose with a residual ammonia content of 3% is dispersed in soda lye (400 ml to 10 g cellulose). This suspension is kept for 1 hour at 20-25~C. The modified cellulose is washed with ethanol after the aqueous soda lye has ~Irst been drawn off. The content of remaining NaOH was 2.5% (related to thecellulose). The washed cellulose is fed into a N-methyl-pyrrolidone ~), which contains 3.9% benzyl-trimethyl ammonium chloride. The suspension is placed under a slight vacuum (20 mbar) at 40~C so as to completely remove the ethanol.
Subsequently, under norrnal pressure, whilst stirring vigorously, a solution of benzyl chloride in NlvIP is added, the molar ratio benzyl chloride/AHG amountingto 2:1. After a reaction time of 1 hour at 40~C, the obtained benzyl cellulose is filtered off and washed with water until a pH value of close on 7 is obtained in the washing water. Subsequently, the benzyl cellulose is dried at a temperature of 80~C under a vacuum of 1 mm Hg. The substitution degree according to infrared spectroscopy was 0.15.

Example 3: Production of benzo~l cellulose 10 g ammonia-exploded cellulose with a residual ammonia content of 7.7% is mixed into 120 ml of a 1~,/o aqueous NaOH-solution for 1 hour at 20-25~C. After drawing off the soda lye (residual soda lye: 2.4%, related to cellulose), the cellulose is mixed with 200 ml N-methyl pyrrolidone and then left to stand for 12 hours to permit an exchange of the NMP by water. Subsequently, the cellulose is largely freed from the water containing NMP by pressing out and is then taken upin pure NMP. Af'cer cooling to 15~C, 3.3% by mass benzyl trimethyl ammonium AO~7~ E
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' CA 02241800 1998-07-03 chloride, related to the cellulose, is added. Subsequently so much benzoyl chloride, dissolved in NMP, is added that the molar ratio to the cellulose amounts to 1:1. The reaction mixture is heated for 3 hours to 50~C, then cooled again and left to stand for 12 hours. The obtained benzoyl cellulose is filtered off and washed with water and then with alcohol. Subsequently a drying takes place ~mdervacuum at 80~C.

Example 4: Production of cyano-ethvl cellulose NH3-activated cellulose with a residual arnmonia content of 3% is dispersed in an aqueous 0.5% soda Iye. This mixture is kept for 1 hour at 5~C, then stirred for 15-30 minutes. Then acrylonitrile is added in a quantity so as to obtain a molar ratio acrylonitrile/AHG of 2:1. After stirring, the reaction rnixture is kept for 1.5 to 3 hours at 45~C, then for approximately 2 hours at 0~C. The mixture is neutralisedwith acetic acid. The cyano-ethyl cellulose is filtered off and washed ~,vith water, then with alcohol. Subsequently the cyano-ethyl cellulose is dried at 80~C undervacuum. The obtained cyano-ethyl cellulose has a substitution degree of 0.28.

Example 5: P~oduction of h~,dro~v-eth-,l cellulose 60 g cellulose (type Modo, DP ~Cuo~an) ~ 570) after the ammonium e~plosion are taken up in 750 ml 2% NaOH and degassed in the rotation evaporator for 30 minutes at a temperature of 25~C under a vacuum of 40 mbar. Then the swollen cellulose is pressed to appro~imately 150 g, mixed with 400 g tert-butanol in a 2 1 round flask on the rotation evaporator and evacuated to approximately 50 mbar.
Subsequently 9 g ~aseous ethylene oxide are added at 25~C within 30 minutes, during which the pressure does not exceed 600 mbar. After 1 h the pressure dropsto approximately 220 mbar. A pressure compensation with respect to atmospheric pressure is carried out with nitrogen, followed by heating to 60~C and stirring for 1 hour. After cooling to 20~C, the reaction mixture is neutralised with acetic acid.
The reaction mixture is poured into 2 1 acetone, filtered off and washed with anacetone/water solution (90%/10%). After drying in the vacuum drying cabinet at f ~ .~E
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':' F~.SPA.OUI, -~ CA 02241800 1998-07-03 90~C/10 mbar up to constant mass, 63 g of hydroxy-ethyl cellulose (DS ~ 0.4) areobtained. The product is completely soluble in water.

E~ample 6: Production of hvdro~v-ethvl cellulose 20 g cellulose (type Modo, DP (Cuoxan) ~ 570) after the ammonium explosion are taken up in 120 ml 2% NaOH and degassed in the rotation evaporator for 30 minutes at a temperature of 25~C under a vacuum of 40 mbar. Then the swollen cellulose is pressed to approximately 60 g, mixed thoroughly with 140 g tert-butanol in a 1 1 stirring autoclave and scavenged with nitrogen. Subsequently 18 g ethylene oxide are added at 25~C, heated ~,vithin 30 minutes to 60~C and stirred for 1 hour. After cooling the autoclave to 20~C the reaction mixture is neutralised with acetic acid. The reaction mixture is poured into 500 ml of a tert-butanol/water solution (80%/20%), filtered off and washed with tert-butanoV~,vater (80%/20%).
After drying in the vacuum drying cabinet at 90~C/10 mbar up to constant mass, 28 g of hydroxy-ethyl cellulose (DS ~ 2.6) are obtained. The product is com-pletely soluble in water.

Example 7: Viscosin~

20 g cellulose (type Viscokraft LV 4, DP (Cuoxan) ~ 400) after the ammonium explosion are taken up in 120 ml 4~/o NaOH and de assed in the rotation evaporator in a 1 1 round flask for 30 minutes at a temperature of 25~C under vacuum (40 mbar). Subsequently 5 g carbon disulphide are metered into the rotating flask at 25-30~C ~,-ithin 5 minutes, during which the pressure increases to approximately 500 mbar. After 2 h the pressure drops to approximately 180 mbar.
Then the flask is cooled by means of an ice bath. After cooling to below 10~C, 80 ml of 8% NaOH are added and stirred for 12 h until a light yellow, clear viscose solution is obtained.

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Claims (9)

claims

1. Process for producing cellulose derivatives, with which a) cellulose is impregnated with an alkali solution, b) the impregnated cellulose is optionally pressed and c) the cellulose is subjected to a substitution or addition reaction, wherein a cellulose derivative with a substitution degree DS is obtained, characterised in that the cellulose used is an ammonia-activated cellulose and the molar ratio of alkali to AHG in the cellulose at the beginning of step c) does not exceed 2 times the DS.

2. Process according to claim 1, characterised in that the alkali solution has a concentration of approximately 12% by mass or less.

3. Process according to claim 3, characterised in that the alkali solution has a concentration of less than approximately 10% by mass.

4. Process according to any one of the claims 1 to 3, characterised in that the molar ratio of alkali to AHG in the cellulose at the beginning of step c) does not exceed 1,5 times the DS.

5. Process according to any one of the claims 1 to 4, characterised in that a sub-stoichiometric ratio of alkali to AHG is maintained in the cellulose.

6. Process according to any one of the preceding claims, characterised in that the ammonia-activated cellulose is obtained by a process with which the cellulose is brought into contact with liquid ammonia at a starting pressure which is higher than atmospheric pressure and at a temperature of at least approximately 25°C, wherein the quantity of the liquid ammonia suffices at least to wet the surface of the cellulose, and that the volume available to the system cellulose/liquid ammonia is increased in an explosion-like manner whilst reducing the pressure by at least 5 bar.

7. Process according to any one of the preceding claims, characterised in that the alkali solution is aqueous or alcoholic soda lye or potassium lye.

8. Process according to any one of the preceding claims, characterised in that the substitution or addition is brought about by reaction with carbon disulphide, acyl-group transferring reagents, alkyl-group transferring reagents, alkene oxides, .alpha.-halocarboxylic acids or their salts, .alpha.,.beta.-unsaturated carbonyl compounds or acrylonitrile.

9. Process according to any one of the preceding claims, characterised in that the cellulose, after impregnation with alkali solution and prior to the substitutionor addition reaction, is not subjected to a pressing step.